Emulsion containing organosilicon-based portions of hollow spheres

ABSTRACT

The present invention relates to a composition in the form of an emulsion containing portions of hollow spheres of organosilicon-based material, the portions of hollow spheres having a mean diameter ranging from 0.05 to 10 μm. The invention also relates to physiologically acceptable emulsion compositions comprising hollow spheres, and to a process for fading out skin surface defects, in particular to reduce the sheen of the skin and/or to fade out pores, shadows under the eyes, marks, wrinkles and/or fine lines, comprising the topical application to the skin of the above-mentioned compositions.

REFERENCE TO PRIOR APPLICATIONS

This application is a continuation application of U.S. application Ser.No. 10/982,925, filed Nov. 8, 2004, and claims priority to U.S.provisional application 60/529,754 filed Dec. 17, 2003, and to Frenchpatent application 0350829 filed Nov. 13, 2003, both incorporated hereinby reference.

FIELD OF THE INVENTION

The present invention relates to a composition in the form of anemulsion comprising portions of hollow spheres, sometimes termed hollowsphere portions herein, of an organosilicon-based material, the sphereshaving a mean diameter ranging from 0.05 to 10 μm.

The invention also relates to physiologically acceptable emulsioncompositions comprising portions of hollow spheres, and to a process forfading out skin surface defects, in particular to reduce the sheen ofthe skin and/or to fade out pores, shadows under the eyes, marks,wrinkles and/or fine lines, comprising the topical application to theskin of the above-mentioned compositions.

Additional advantages and other features of the present invention willbe set forth in part in the description that follows and in part willbecome apparent to those having ordinary skill in the art uponexamination of the following or may be learned from the practice of thepresent invention. The advantages of the present invention may berealized and obtained as particularly pointed out in the appendedclaims. As will be realized, the present invention is capable of otherand different embodiments, and its several details are capable ofmodifications in various obvious respects, all without departing fromthe present invention. The description is to be regarded as illustrativein nature, and not as restrictive.

BACKGROUND OF THE INVENTION

When the light hits the surface of the skin, it separates into twocomponents: a transmitted component and a reflected component. Thetransmitted light is itself divided into a component of specular ordirect transmission (at a single angle) and a component of diffusetransmission (in all directions). The reflected light is also dividedinto a component of diffuse reflection (in all directions) and acomponent of specular reflection (at a single angle).

It is known that, depending on their size, shape and chemical nature,pulverulent materials interfere with the various components of lightabove and as a result have the capacity to modify the appearance of theskin.

Research has become focused in recent years on powders with high diffusereflectance, low specular reflectance and high diffuse transmittance,which make it possible especially to reduce the appearance of wrinklesand fine lines by reducing the difference in luminosity between thevalley and the edges of wrinkles.

These powders, known as “soft-focus” powders, also make it possible togive shiny skins a more matt appearance.

Now, obtaining a matt effect on the skin is highly sought by users withcombination or greasy skin, and also for cosmetic compositions intendedto be used in hot and humid climates. The reason for this is that thehighlights caused by an excess of sebum on the surface of the skin aregenerally considered as unattractive.

Among the soft-focus powders proposed in the prior art, mention may bemade of certain micas coated with minerals and/or with PMMA, optionallycoated silica microspheres, nylon powders, boron nitride, or talc with agranulometry (or mean particle size) of 1.8 microns.

It nevertheless remains that there is still a need for materials thatallow the surface defects of the skin to be camouflaged.

SUMMARY OF THE INVENTION

The inventor has now discovered, surprisingly and unexpectedly, thatportions of certain silicone particles, including those obtained bycondensation of silanols resulting from the hydrolysis oforganosilicon-based compounds, make it possible to satisfy this needwhen they are formulated as an emulsion.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

One subject of the present invention is thus a composition in the formof an emulsion comprising, preferably in a physiologically acceptablemedium, portions of hollow spheres comprising, consisting essentiallyof, or consisting of, organosilicon-based material, the spheres having amean diameter ranging from 0.05 to 10 μm. In preferred embodiments theportions of hollow spheres consist of organosilicon-based material.

The invention also relates to a process for fading out surface defectsof the skin, especially of greasy or combination skin or aged skin, inparticular to reduce the sheen of the skin and/or to fade out pores,shadows under the eyes, marks, wrinkles and/or fine lines, comprisingthe topical application to the skin of the above-mentioned composition.

The emulsions of the invention are preferably products with a non-greasyfeel in which the optical properties are exploited to camouflage skinimperfections, wherein optional skincare active agents might possiblyact simultaneously on the causes of these imperfections.

Invention particles, which have the form of hollow spheres, have alreadybeen described in patent applications JP-2003 128 788 and JP-2000 191789. In these patent applications, it is suggested to use themespecially in cosmetic products for the face or in makeup products, inparticular in foundation compact powders. For an application in themakeup field, these particles may be formulated in the presence of waterand surfactants. However, it is not suggested to use them in emulsions.

For the purposes of the present invention, the term “emulsion” means asystem comprising at least two phases of two or more immiscible orpartially miscible liquids, one of which—which forms the dispersedphase—is dispersed in the other—which forms the continuous phase—in theform of fine droplets whose diameter generally does not exceed 5microns.

For the purposes of the present invention, the terms “portions of hollowspheres,” and “hollow sphere portions,” mean the same thing and refer toa portion, or part, of a hollow sphere. Such portions or parts may haveany shape, such as the shape of a cup, bowl, vase, etc., and arepreferably substantially hemispherical, understanding that the spherescan be cut across at any height, thus providing, e.g., portions in theform of truncated hollow spheres, with a single orifice communicatingwith their central cavity, and having a transverse cross section in theform of a horseshoe or a bow. Preferably, the portions of hollow spheresconsist of organosilicon material.

The silicon material constituting these hollow sphere portions, in wholeor in part, is preferably a crosslinked polysiloxane ofthree-dimensional structure; it preferably comprises, or even consistsof, units of formula (I): SiO₂ and of formula (II): R¹SiO_(1.5)

in which R¹ denotes an organic group containing a carbon atom directlylinked to the silicon atom. The organic group may be a reactive organicgroup or an unreactive organic group, and preferably an unreactiveorganic group.

The unreactive organic group may be a C₁-C₄ alkyl group, especially amethyl, ethyl, propyl or butyl group, or a phenyl group, and preferablya methyl group.

The reactive organic group may be an epoxy group, a (meth)acryloxygroup, an alkenyl group, a mercaptoalkyl, aminoalkyl or haloalkyl group,a glyceroxy group, a ureido group or a cyano group. Preferably, thereactive organic group may be an epoxy group, a (meth)acryloxy group, analkenyl group or a mercaptoalkyl or aminoalkyl group. The reactiveorganic group generally contains from 2 to 6 carbon atoms and especiallyfrom 2 to 4 carbon atoms.

Epoxy groups that may be mentioned include a 2-glycidoxyethyl group, a3-glycidoxypropyl group or a 2-(3,4-epoxycyclohexyl)propyl group.

(Meth)acryloxy groups that may be mentioned include a3-methacryloxypropyl group or a 3-acryloxypropyl group.

Alkenyl groups that may be mentioned include a vinyl, allyl orisopropenyl group.

Mercaptoalkyl groups that may be mentioned include a mercaptopropyl ormercaptoethyl group.

Aminoalkyl groups that may be mentioned include a3-(2-aminoethyl)aminopropyl group, a 3-aminopropyl group or anN,N-dimethylaminopropyl group.

Haloalkyl groups that may be mentioned include a 3-chloropropyl group ora trifluoropropyl group.

Glyceroxy groups that may be mentioned include a 3-glyceroxypropyl groupor a 2-glyceroxyethyl group.

A ureido group that may be mentioned is a 2-ureidoethyl group.

Cyano groups that may be mentioned include a cyanopropyl or cyanoethylgroup.

Preferably, R₁ denotes a methyl group.

Portinos of hollow spheres that are useful herein include those that maybe obtained according to a process that comprises:

(a) introducing into an aqueous medium, in the presence of at least onehydrolysis catalyst, and optionally of at least one surfactant, acompound (I) of formula SiX₄ and a compound (II) of formula RSiY₃, inwhich X and Y independently denote a C₁-C₄ alkoxy group, an alkoxyethoxygroup containing a C₁-C₄ alkoxy group, a C₂-C₄ acyloxy group, anN,N-dialkylamino group containing a C₁-C₄ alkyl group, a hydroxyl group,a halogen atom or a hydrogen atom, and R denotes an organic groupcomprising a carbon atom directly linked to the silicon atom andespecially has the meaning given above for R₁; and(b) placing the mixture resulting from step (a) in contact with anaqueous solution containing at least one polymerization catalyst andoptionally at least one surfactant, at a temperature of between 30 and85° C., for at least two hours.

Step (a) can be termed a hydrolysis reaction and step (b) a condensationreaction.

As regards the groups X and Y of compounds (I) and (II), the followingmay be used:

-   -   as C₁-C₄ alkoxy groups: methoxy or ethoxy groups;    -   as alkoxyethoxy groups containing a C₁-C₄ alkoxy group:

methoxyethoxy or butoxyethoxy groups;

-   -   as C₂-C₄ alkyloxy groups: acetoxy or propoxy groups;    -   as N,N-dialkylamino groups containing a C₁-C₄ alkyl group:        dimethylamino or diethylamino groups;    -   as halogen atoms: chlorine or bromine atoms.

Preferably, X and/or Y denotes a C₁-C₄ alkoxy group.

Thus, preferred compounds of formula (I) that may be mentioned include:tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane,trimethoxyethoxysilane, tributoxyethoxysilane, tetraacetoxysilane,tetra-propoxysilane, tetraacetoxysilane, tetra(dimethylamino)silane,tetra(diethylamino)silane, silane tetraol, chlorosilane triol,dichlorodisilanol, tetrachlorosilane, chlorotrihydrogenosilane.Preferably, the compound of formula (I) is selected from the groupconsisting of tetramethoxysilane, tetraethoxysilane andtetrabutoxysilane, and mixtures thereof.

Preferred compounds of formula (II) comprising an unreactive organicgroup R that may be mentioned include: methyltrimethoxysilane,ethyltriethoxysilane, propyltributoxysilane, butyltributoxysilane,phenyl-trimethoxyethoxysilane, methyltributoxyethoxysilane,methyltriacetoxysilane, methyltripropoxysilane, methyltriacetoxysilane,methyltri(dimethylamino)silane, methyltri(diethylamino)silane,methylsilane triol, methylchlorodisilanol, methyltrichlorosilane andmethyltrihydrogenosilane.

Finally, preferred compounds of formula (II) comprising a reactiveorganic group R that may be mentioned include:

silanes containing an epoxy group, for instance 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl triethoxysilane,2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyl dimethoxysilane,2-glycidoxyethylmethyl dimethoxysilane, 3-glycidoxypropyldimethylmethoxysilane and 2-glycidoxyethyl dimethylmethoxysilane;silanes containing a (meth)acryloxy group, for instance3-methacryloxypropyl trimethoxysilane and 3-acryloxypropyltrimethoxysilane;silanes containing an alkenyl group, for instance vinyltrimethoxysilane, allyl trimethoxysilane and isopropenyltrimethoxysilane;silanes containing a mercapto group, for instance mercaptopropyltrimethoxysilane and mercaptoethyl trimethoxysilane;silanes containing an aminoalkyl group, for instance 3-aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyl trimethoxysilane,N,N-dimethylaminopropyl trimethoxysilane and N,N-dimethylaminoethyltrimethoxysilane;silanes containing a haloalkyl group, for instance 3-chloropropyltrimethoxysilane and trifluoropropyl trimethoxysilane;silanes containing a glyceroxy group, for instance 3-glyceroxypropyltrimethoxysilane and bis(3-glyceroxypropyl)dimethoxysilane;silanes containing a ureido group, for instance 3-ureidopropyltrimethoxysilane, 3-ureidopropyl methyldimethoxysilane and3-ureidopropyl dimethylmethoxysilane;silanes containing a cyano group, for instance cyanopropyltrimethoxysilane, cyanopropyl methyldimethoxysilane and cyanopropyldimethylmethoxysilane.

Highly preferred examples of compounds of this type of formula (II) areselected from the group consisting of: silanes containing an epoxygroup, silanes containing a (meth)acryloxy group, silanes containing analkenyl group, silanes containing a mercapto group and silanescontaining an aminoalkyl group.

Examples of compounds (I) and (II) that are highly preferred forperforming this invention are, respectively, tetraethoxysilane andmethyltrimethoxysilane. After polymerization of these units, the sphereportions according to the invention thus advantageously have acrosslinked structure consisting of SiO₂ units and of R₁ SiO_(1.5) unitsin which R₁ is preferably a methyl group.

In step (a), the molar ratio of compound (I) to compound (II) usuallyranges from 30:70 to 50:50, advantageously from 35:65 to 45:55 and ispreferably 40:60. The weight ratio of water to the total amount ofcompounds (I) and (II) preferably ranges from 10:90 to 70:30. The orderof introduction of compounds (I) and (II) generally depends on theirrate of hydrolysis. The temperature of the hydrolysis reaction usuallyranges from 0° C. to 40° C. and usually does not exceed 30° C. so as toavoid premature condensation of the compounds.

Hydrolysis and polymerization catalysts that may be used include basiccatalysts—such as sodium hydroxide, sodium carbonate or amines- oracidic catalysts, selected from the group consisting of organicacids—such as acetic acid or sodium dodecylbenzenesulfonate- or mineralcatalysts—such as hydrochloric acid. When it is present, the surfactantis preferably a nonionic or anionic surfactant or a mixture of the two.Sodium dodecylbenzenesulfonate may be used as anionic surfactant. Theend of hydrolysis is marked by the disappearance of the water-insolubleproducts (I) and (II), and the production of a homogeneous liquid layer.

The condensation step (b) can use the same catalyst as the hydrolysisstep and/or another catalyst selected from the group consisting of thosementioned above.

After this process, a suspension in water of fine organosilicon-basedparticles is obtained, which may then optionally be separated from theirmedium. The process described above can thus include an additionalfiltration step, for example through a membrane filter, of the productresulting from step (b), optionally followed by a step of centrifugationof the filtrate, which is intended to separate the particles from theliquid medium, and then a step of drying the particles. Needless to say,other separation methods may be used.

The spheres obtained have a mean diameter ranging from 0.05 to 10 μm.

The form and dimensions of the hollow sphere portions obtained accordingto the above process will depend especially on the mode of bringing theproducts into contact in step (b).

A rather basic pH and cold introduction of the polymerization catalystinto the mixture obtained in step (a) will lead to hollow sphereportions in the form of round-bottomed “bowls”, whereas a rather acidicpH and dropwise introduction of the mixture obtained in step (a) intothe hot polymerization catalyst will lead to hollow sphere portionshaving a transverse cross section in the form of a “horseshoe”.

According to one preferred embodiment of the invention, hollow sphereportions in the form of “bowls” are used. These may be obtained asdescribed in patent application JP-2003 128 788.

The attached FIGURE illustrates sphere portions of this type intransverse cross section.

As is seen from this FIGURE, these sphere portions are formed (inlongitudinal cross section) from a small inner arc (11), a large outerarc (21) and segments (31) linking the ends of the respective arcs, thewidth (W1) between the two ends of the small inner arc (11) ranging from0.01 to 8 μm and preferably from 0.02 to 6 μm on average, the width (W2)between the two ends of the large outer arc (21) ranging from 0.05 to 10μm on average and the height (H) of the large outer arc (21) rangingfrom 0.015 to 8 μm on average. The segments (31) preferably have alength (W2−W1)/2 (referred to hereinbelow as the “particle thickness”)ranging from 0.05 to 1 μm and more preferably from 0.1 to 0.8 μm.

The dimensions mentioned above are obtained by calculating the averagedimensions of one hundred particles selected from the group consistingof an image obtained using a scanning electron microscope.

According to one advantageous embodiment of the invention, the ratio Raof the width W2 to the thickness (W2−W1)/2 is at least equal to 3,preferably greater than 5 and better still greater than 10, or evengreater than 20. Specifically, the inventor has discovered that thehigher this ratio, the better the optical properties of the materialsaccording to the invention and the smaller the amount of materialrequired to obtain a desired effect.

As sphere portions that may be used according to the invention, mentionmay be made of the bowl-shaped particles sold in the series NLK by thecompany Takemoto Oil & Fat, which consist of crosslinked organosiliconeTAK-110 (methylsilanol/silicate crosslinked polymer) from this samecompany, in particular the particles sold under the name NLK-506.

The amount of sphere portions used in the composition according to theinvention is not limited and can represent, for example, from 0.1% to20%, preferably from 0.5% to 15% and better still from 0.5% to 10% ofthe total weight of the composition.

The composition according to the invention is preferably suitable fortopical application to the skin and thus generally comprises aphysiologically acceptable medium, i.e. a medium that is compatible withthe skin and possibly with its integuments. Preferably, it is acosmetically acceptable medium, i.e. a medium that has a pleasantappearance, in particular colour, odour and feel, and that does notcause discomfort (redness, stinging or tautness) liable to put the useroff the composition.

The composition according to the invention may be in the form of anemulsion obtained by dispersing an aqueous phase in a fatty phase (W/O)or a fatty phase in an aqueous phase (O/W), of liquid or semi-liquidconsistency of the milk type, or of soft, semi-solid or solidconsistency of the cream or gel type, or alternatively a multipleemulsion (W/O/W or O/W/O). These compositions can prepared according tothe usual methods known to those of ordinary skill in this art in viewof this disclosure.

The composition according to the invention may be in the form of a careor makeup product for the face and/or the body, and may be packaged, forexample, in the form of cream in a jar or fluid in a tube or in apump-dispenser bottle.

According to one preferred embodiment of the invention, the compositionis in the form of an O/W emulsion.

As non-limiting examples of oils that may be used in the composition ofthe invention, mention may be made of:

-   -   hydrocarbon-based oils of animal origin, such as        perhydrosqualene;    -   hydrocarbon-based oils of plant origin, such as liquid        triglycerides of fatty acids containing from 4 to 10 carbon        atoms, for instance heptanoic or octanoic acid triglycerides or        alternatively, for example, sunflower oil, maize oil, soybean        oil, marrow oil, grapeseed oil, sesame seed oil, hazelnut oil,        apricot oil, macadamia oil, arara oil, sunflower oil, castor        oil, avocado oil, caprylic/capric acid triglycerides, for        instance those sold by the company Stearineries Dubois or those        sold under the names Miglyol 810, 812 and 818 by the company        Dynamit Nobel, jojoba oil or shea butter oil;    -   synthetic esters and synthetic ethers, especially of fatty        acids, for instance oils of formulae R¹COOR² and R¹OR² in which        R¹ represents the fatty acid residue containing from 8 to 29        carbon atoms and R² represents a branched or unbranched        hydrocarbon-based chain containing from 3 to 30 carbon atoms,        such as, for example, purcellin oil, isononyl isononanoate,        isopropyl myristate, 2-ethylhexyl palmitate, 2-octyldodecyl        stearate, 2-octyldodecyl erucate or isostearyl isostearate;        hydroxylated esters such as isostearyl lactate, octyl        hydroxystearate, octyldodecyl hydroxystearate, diisostearyl        malate, triisocetyl citrate and fatty alkyl heptanoates,        octanoates and decanoates; polyol esters, for instance propylene        glycol dioctanoate, neopentyl glycol diheptanoate and diethylene        glycol diisononanoate; and pentaerythritol esters, for instance        pentaerythrityl tetraisostearate;    -   linear or branched hydrocarbons of mineral or synthetic origin,        such as volatile or non-volatile paraffin oils, and derivatives        thereof, isohexadecane, isododecane, petroleum jelly,        polydecenes, and hydrogenated polyisobutene such as Parleam®        oil;    -   natural or synthetic essential oils such as, for example,        eucalyptus oil, lavandin oil, lavender oil, vetiver oil, Litsea        cubeba oil, lemon oil, sandalwood oil, rosemary oil, camomile        oil, savory oil, nutmeg oil, cinnamon oil, hyssop oil, caraway        oil, orange oil, geraniol oil, cade oil and bergamot oil;    -   fatty alcohols containing from 8 to 26 carbon atoms, for        instance cetyl alcohol, stearyl alcohol and the mixture thereof        (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol,        2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol or linoleyl        alcohol;    -   partially hydrocarbon-based and/or partially silicone-based        fluoro oils, for instance those described in document JP-A-2 295        912;    -   silicone oils, for instance volatile or non-volatile        polymethylsiloxanes (PDMSs) containing a linear or cyclic        silicone chain, that are liquid or pasty at room temperature,        especially cyclopolydimethylsiloxanes (cyclomethicones) such as        cyclohexasiloxane and cyclopentasiloxane; poly-dimethylsiloxanes        comprising alkyl, alkoxy or phenyl groups, that are pendant or        at the end of a silicone chain, these groups containing from 2        to 24 carbon atoms; phenylsilicones, for instance        phenyltrimethicones, phenyldimethicones,        phenyltrimethylsiloxydiphenylsiloxanes, diphenyldimethicones,        diphenylmethyl-diphenyltrisiloxanes,        2-phenylethyltrimethylsiloxysilicates and        polymethylphenylsiloxanes;    -   mixtures thereof.

In the list of oils mentioned above, the expression “hydrocarbon-basedoil” means any oil mainly comprising carbon and hydrogen atoms, andoptionally ester, ether, fluoro, carboxylic acid and/or alcohol groups.The other fatty substances that may be present in the oily phaseinclude, for example, fatty acids containing from 8 to 30 carbon atoms,for instance stearic acid, lauric acid, palmitic acid and oleic acid;waxes, for instance lanolin, beeswax, carnauba wax or candelilla wax,paraffin waxes, lignite wax or microcrystalline waxes, ceresin orozokerite, synthetic waxes such as polyethylene waxes, Fischer-Tropschwaxes; gums such as silicone gums (dimethiconol); silicone resins suchas trifluoromethyl-C1-4-alkyldimethicone andtrifluoropropyl-dimethicone; and silicone elastomers, for instance theproducts sold under the name “KSG” by the company Shin-Etsu, under thename “Trefil”, “BY29” or “EPSX” by the company Dow Corning, or under thename “Gransil” by the company Grant Industries.

These fatty substances may be chosen in a varied manner by a personskilled in the art so as to prepare a composition having the desiredproperties, for example in terms of consistency or texture, in view ofthis disclosure.

When it is present, the amount of oily phase is not limited and mayrange, for example, from 0.01% to 50% by weight and preferably from 0.1%to 30% by weight relative to the total weight of the composition.

According to one particularly advantageous embodiment of the invention,the composition comprises at least one volatile oil. Specifically, theinventor has demonstrated that this type of oil improves the opticalproperties of the composition comprising the organosilicon-based openhollow sphere portions described above.

The expression “volatile oils” means oils having, at a temperature of20° C., a vapour pressure of greater than 1 mbar. The vapour pressure isdefined as being the pressure at which a liquid and its vapour are inequilibrium at a given temperature. Useful volatile oils that may bementioned, inter alia, include cyclic or linear silicones containingfrom 2 to 6 silicon atoms, such as cyclohexasiloxane,dodecamethylpentasiloxane, decamethyltetrasiloxane,octamethyltrisiloxane and hexamethyldisiloxane. Mention may also be madeof branched hydrocarbons, for instance isododecanes, and also volatileperfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane,sold under the names “PF 5050®” and “PF 5060®” by the company 3M, andperfluoromorpholine derivatives, such as 4-trifluoromethylperfluoromorpholine sold under the name “PF 5052®” by the company 3M.

The composition according to the invention may also contain variousadjuvants such as those commonly used in cosmetics, such as emulsifiers;fillers; sequestering agents; colorants; fragrances; and thickeners andgelling agents. The amounts and nature of these various adjuvants ispreferably chosen so as not to harm the optical properties of thecomposition.

The emulsions generally contain at least one emulsifier selected fromthe group consisting of amphoteric, anionic, cationic and nonionicemulsifiers, used alone or as a mixture, and optionally a co-emulsifier.The emulsifiers are chosen in a suitable manner depending on theemulsion to be obtained (e.g., W/O or O/W). The emulsifier and theco-emulsifier are generally present in the composition in a proportionthat may range, for example, from 0.3% to 30% by weight and preferablyfrom 0.5% to 20% by weight relative to the total weight of thecomposition.

Examples of emulsifiers that may be mentioned for the W/O emulsionsinclude dimethicone copolyols such as the mixture of cyclomethicone andof dimethicone copolyol, sold under the name “DC 5225 C” by the companyDow Corning, and alkyldimethicone copolyols, such as the laurylmethiconecopolyol sold under the name “Dow Corning 5200 Formulation Aid” by thecompany Dow Corning, the cetyldimethicone copolyol sold under the nameAbil EM 90® by the company Goldschmidt, or the mixture ofcetyldimethicone copolyol, polyglyceryl-4 isostearate and hexyl laurate,sold under the name Abil WE09® by the company Goldschmidt. One or moreco-emulsifiers may also be added thereto, which may be advantageouslyselected from the group consisting of the group comprising alkylatedesters of polyol. Alkylated esters of polyol that may especially bementioned include glycerol and/or sorbitan esters, for examplepolyglyceryl isostearate, such as the product sold under the name IsolanGI 34 by the company Goldschmidt, sorbitan isostearate, such as theproduct sold under the name Arlacel 987 by the company ICI, sorbitanglyceryl isostearate, such as the product sold under the name Arlacel986 by the company ICI, and mixtures thereof.

Surfactants for W/O emulsions that may also be used include acrosslinked elastomeric solid organopolysiloxane comprising at least oneoxyalkylene group, such as those obtained according to the procedure ofExamples 3, 4 and 8 of document U.S. Pat. No. 5,412,004 and of theexamples of document U.S. Pat. No. 5,811,487, especially the product ofExample 3 (synthesis example) of U.S. Pat. No. 5,412,004, and such asthe product sold under the reference KSG 21 by the company Shin-Etsu.

Examples of emulsifiers that may be mentioned for the O/W emulsionsinclude nonionic surfactants, and especially esters of polyols and offatty acids with a saturated or unsaturated chain containing, forexample, from 8 to 24 carbon atoms and better still from 12 to 22 carbonatoms, and the oxyalkylenated derivatives thereof, i.e. derivativescontaining oxyethylenated and/or oxypropylenated units, such as theglyceryl esters of C₈-C₂₄ fatty acids, and the oxyalkylenatedderivatives thereof the polyethylene glycol esters of C₈-C₂₄ fattyacids, and the oxyalkylenated derivatives thereof; the sorbitol estersof C₈-C₂₄ fatty acids, and the oxyalkylenated derivatives thereof; thesugar (sucrose, glucose or alkylglucose) esters of C₈-C₂₄ fatty acids,and the oxyalkylenated derivatives thereof; the ethers of fattyalcohols; the sugar ethers of C₈-C₂₄ fatty alcohols, and mixturesthereof.

Glyceryl esters of fatty acids that may especially be mentioned includeglyceryl stearate (glyceryl mono-, di- and/or tristearate) (CTFA name:glyceryl stearate) or glyceryl ricinoleate and mixtures thereof.

Polyethylene glycol esters of fatty acids that may especially bementioned include polyethylene glycol stearate (polyethylene glycolmono-, di- and/or tristearate) and more especially polyethylene glycol50 OE monostearate (CTFA name: PEG-50 stearate), polyethylene glycol 100OE monostearate (CTFA name: PEG-100 stearate) and mixtures thereof.

It is also possible to use mixtures of these surfactants, for instancethe product containing glyceryl stearate and PEG-100 stearate, soldunder the name Arlacel 165 by the company Uniqema, and the productcontaining glyceryl stearate (glyceryl mono-distearate) and potassiumstearate, sold under the name Tegin by the company Goldschmidt (CTFAname: glyceryl stearate SE).

Fatty acid esters of glucose or of alkylglucose that may be mentioned inparticular include glucose palmitate, alkylglucose sesquistearates, forinstance methyl glucose sesquistearate, alkylglucose palmitates, forinstance methylglucose palmitate or ethylglucose palmitate, fatty estersof methylglucoside and more especially the diester of methylglucosideand of oleic acid (CTFA name: Methyl glucose dioleate); the mixed esterof methylglucoside and of the oleic acid/hydroxystearic acid mixture(CTFA name: Methyl glucose dioleate/hydroxysterate); the ester ofmethylglucoside and of isostearic acid (CTFA name: Methyl glucoseisostearate); the ester of methylglucoside and of lauric acid (CTFAname: Methyl glucose laurate); the mixture of the monoester and diesterof methylglucoside and of isostearic acid (CTFA name: Methyl glucosesesquiisostearate); the mixture of the monoester and diester ofmethylglucoside and of stearic acid (CTFA name: Methyl glucosesesquistearate) and in particular the product sold under the nameGlucate SS by the company Amerchol, and mixtures thereof.

Examples of oxyethylenated ethers of a fatty acid and of glucose or ofalkylglucose that may be mentioned include the oxyethylenated ethers ofa fatty acid and of methylglucose, and in particular the polyethyleneglycol ether of the diester of methyl glucose and of stearic acidcontaining about 20 mol of ethylene oxide (CTFA name: PEG-20 methylglucose distearate), such as the product sold under the name Glucam E-20distearate by the company Amerchol; the polyethylene glycol ether of themixture of monoester and diester of methylglucose and of stearic acidcontaining about 20 mol of ethylene oxide (CTFA name: PEG-20 methylglucose sesquistearate) and in particular the product sold under thename Glucamate SSE-20 by the company Amerchol, and the product soldunder the name Grillocose PSE-20 by the company Goldschmidt, andmixtures thereof.

Examples of sucrose esters that may be mentioned include sucrosepalmitostearate, sucrose stearate and sucrose monolaurate.

Examples of ethers of fatty alcohols that may be mentioned includepolyethylene glycol ethers of fatty alcohols containing from 8 to 30carbon atoms and especially from 10 to 22 carbon atoms, such aspolyethylene glycol ethers of cetyl alcohol, stearyl alcohol or cetearylalcohol (mixture of cetyl and stearyl alcohol). Examples that may bementioned include ethers comprising from 1 to 200 and preferably from 2to 100 oxyethylene groups, such as those of CTFA name Ceteareth-20 andCeteareth-30, and mixtures thereof.

Sugar ethers that may especially be mentioned includealkylpolyglucosides, for example decylglucoside, for instance theproduct sold under the name Mydol 10 by the company Kao Chemicals, theproduct sold under the name Plantaren 2000 by the company Henkel, andthe product sold under the name Oramix NS 10 by the company SEPPIC;caprylyl/capryl glucoside, for instance the product sold under the nameOramix CG 110 by the company SEPPIC or under the name Lutensol GD 70 bythe company BASF; laurylglucoside, for instance the products sold underthe names Plantaren 1200 N and Plantacare 1200 by the company Henkel;cocoglucoside, for instance the product sold under the name Plantacare818/UP by the company Henkel; cetostearyl glucoside optionally as amixture with cetostearyl alcohol, sold, for example, under the nameMontanov 68 by the company SEPPIC, under the name Tego-Care CG90 by thecompany Goldschmidt and under the name Emulgade KE3302 by the companyHenkel; arachidyl glucoside, for example in the form of the mixture ofarachidyl alcohol and behenyl alcohol and arachidyl glucoside, soldunder the name Montanov 202 by the company SEPPIC; cocoylethylglucoside,for example in the form of a mixture (35/65) with cetyl and stearylalcohol, sold under the name Montanov 82 by the company SEPPIC, andmixtures thereof.

As indicated above, depending on the fluidity of the composition that itis desired to obtain, one or more gelling agents, especially hydrophilicgelling agents, i.e. water-soluble or water-dispersible gelling agents,may be incorporated into the composition.

Hydrophilic gelling agents that may be mentioned in particular includewater-soluble or water-dispersible thickening polymers. These polymersmay be chosen especially from: modified or unmodified carboxyvinylpolymers, such as the products sold under the names Carbopol (CTFA name:carbomer) and Pemulen (CTFA name: Acrylates/C10-30 alkyl acrylatecrosspolymer) by the company Goodrich; polyacrylates andpolymethacrylates such as the products sold under the names Lubrajel andNorgel by the company Guardian or under the name Hispagel by the companyHispano Chimica; polyacrylamides; optionally crosslinked and/orneutralized 2-acrylamido-2-methylpropane sulfonic acid polymers andcopolymers, for instance the poly(2-acrylamido-2-methylpropane-sulfonicacid) sold by the company Clariant under the name “Hostacerin AMPS”(CTFA name: ammonium polyacryldimethyltauramide); crosslinked anioniccopolymers of acrylamide and of AMPS, which are in the form of a W/Oemulsion, such as those sold under the name Sepigel 305 (CTFA name:Polyacrylamide/C13-14 Isoparaffin/Laureth-7) and under the name Simulgel600 (CTFA name: Acrylamide/Sodium acryloyldimethyltauratecopolymer/Isohexadecane/Polysorbate 80) by the company SEPPIC;polysaccharide biopolymers, for instance xanthan gum, guar gum, carobgum, acacia gum, scleroglucans, chitin and chitosan derivatives,carrageenans, gellans, alginates, celluloses such as microcrystallinecellulose, carboxymethylcellulose, hydroxymethylcellulose andhydroxypropylcellulose; and mixtures thereof.

Examples of lipophilic gelling agents that may be mentioned includemodified clays such as modified magnesium silicate (Bentone Gel VS38from Rheox), or hectorite modified with distearyldimethylammoniumchloride (CTFA name: Disteardimonium hectorite) sold under the nameBentone 38 CE by the company Rheox.

As mentioned previously, the composition according to the invention mayalso comprise fillers, possibly having a matting effect capable ofreinforcing the effects of the sphere portions according to theinvention.

Examples of fillers that may be mentioned include polyamide (Nylon)particles and especially the microbeads sold under the name Orgasol bythe company Atochem, or nylon fibres; polyethylene powders; microspheresbased on acrylic copolymers, such as those made of ethylene glycoldimethacrylate/lauryl methacrylate copolymer sold by the company DowCorning under the name Polytrap; the polymethyl methacrylatemicrospheres sold under the name Microsphere M-100 by the companyMatsumoto or under the name Covabead LH 85 by the company Wackherr;melamine-formaldehyde or urea-formaldehyde resin particles;poly(tetrafluoroethylene) particles; ethylene-acrylate copolymerpowders, for instance those sold under the name Flobeads by the companySumitomo Seika Chemicals; expanded powders such as hollow microspheresand especially microspheres formed from a terpolymer of vinylidenechloride, acrylonitrile and methacrylate, and sold under the nameExpancel by the company Kemanord Plast under the references 551 DE 12(particle size of about 12 μm and mass of a unit volume of 40 kg/m³),551 DE 20 (particle size of about 30 μm and mass of a unit volume of 65kg/m³) and 551 DE 50 (particle size of about 40 μm), or thepolyacrylonitrile microspheres sold under the name Micropearl F 80 ED bythe company Matsumoto; powders of natural organic materials such asstarch powders, especially of crosslinked or non-crosslinked maize,wheat or rice starch, such as the powders of starch crosslinked withoctenylsuccinate anhydride, sold under the name Dry-Flo by the companyNational Starch, or cellulose microbeads; silicone resin microbeads,such as those sold under the name Tospearl by the company ToshibaSilicone, especially Tospearl 240; and mixtures thereof.

Other examples of matting agents that may be used in the compositionaccording to the invention include polymers comprising units with anLCST, as described in patent application FR-2 838 345; copolymers ofvinylpyrrolidone and of 1-triacontene; and clays.

To reinforce the effects of the composition according to the invention,it may also, or as a variant, contain one or more active agents thatcomplement the effect obtained using the silicone-based hollow sphereportions.

For an application in particular in caring for or making up greasy skin,the composition according to the invention may comprise at least oneactive agent selected from the group consisting of: desquamating agents,anti-seborrhoeic agents, antimicrobial agents and calmatives.

For an application in particular in caring for or making up aged skin,the composition according to the invention may comprise at least oneactive agent selected from the group consisting of: desquamating agentsor moisturizers; depigmenting or anti-pigmenting agents; anti-glycationagents; anti-NO agents; agents for stimulating the synthesis of dermalor epidermal macromolecules and/or for preventing their degradation;agents for stimulating fibroblast or keratinocyte proliferation and/orkeratinocyte differentiation; muscle relaxants or dermo-decontractingagents; free-radical scavengers or anti-pollution agents; tensioningagents; and agents acting on the capillary circulation.

Non-limiting examples of such active agents will now be given.

1. Desquamating Agents and Moisturizers

The term “desquamating agent” means any compound capable of acting:

either directly on desquamation by promoting exfoliation, such asβ-hydroxy acids, in particular salicylic acid and its derivatives(including 5-n-octanoylsalicylic acid); α-hydroxy acids, such asglycolic acid, citric acid, lactic acid, tartaric acid, malic acid ormandelic acid; urea; gentisic acid; oligofucoses; cinnamic acid; extractof Saphora japonica; resveratrol and certain jasmonic acid derivatives;

or on the enzymes involved in the desquamation or degradation ofcorneodesmosomes, glycosidases, stratum corneum chymotryptic enzyme(SCCE), or even other proteases (trypsin, chymotrypsin-like). Mentionmay be made of agents for chelating mineral salts: EDTA;N-acyl-N,N′,N′-ethylenediaminetriacetic acid; aminosulfonic compoundsand in particular (N-2-hydroxyethylpiperazine-N-2-ethane)sulfonic acid(HEPES); 2-oxothiazolidine-4-carboxylic acid (procysteine) derivatives;α-amino acid derivatives of the type such as glycine (as described inEP-0 852 949 and sodium methylglycinediacetate sold by BASF under thetrade name Trilon M); honey; sugar derivatives such asO-octanoyl-6-D-maltose and N-acetylglucosamine.

The term “moisturizer” means:

either a compound acting on the barrier function, in order to keep thestratum corneum moisturized, or an occlusive compound. Mention may bemade of ceramides, sphingoid-based compounds, lecithins,glycosphingolipids, phospholipids, cholesterol and its derivatives,phytosterols (stigmasterol, β-sitosterol or campesterol), essentialfatty acids, 1,2-diacylglycerol, 4-chromanone, pentacyclic triterpenessuch as ursolic acid, petroleum jelly and lanolin;

or a compound that directly increases the water content of the stratumcorneum, such as threalose and its derivatives, hyaluronic acid and itsderivatives, glycerol, pentanediol, sodium pidolate, serine, xylitol,sodium lactate, polyglyceryl acrylate, ectoin and its derivatives,chitosan, oligosaccharides and polysaccharides, cyclic carbonates,N-lauroylpyrrolidonecarboxylic acid and N-α-benzoyl-L-arginine;

or a compound that activates the sebaceous glands, such as steroidderivatives (including DHEA the 7-oxido and/or 17-alkyl derivativesthereof, and sapogenins), methyl dihydrojasmonate and vitamin D and itsderivatives.

2. Depigmenting, Anti-Pigmenting or Pro-Pigmenting Agent

The depigmenting or anti-pigmenting agents that may be incorporated intothe composition according to the present invention comprise, forexample, the following compounds: kojic acid; ellagic acid; arbutin andits derivatives such as those described in patent applications EP-895779 and EP-524 109; hydroquinone; aminophenol derivatives such as thosedescribed in patent applications WO 99/10318 and WO 99/32077, and inparticular N-cholesteryloxycarbonyl-para-aminophenol andN-ethyloxycarbonyl-para-aminophenol; iminophenol derivatives, inparticular those described in patent application WO 99/22707;L-2-oxothiazolidine-4-carboxylic acid or procysteine, and also its saltsand esters; calcium D-pantheteine sulfonate; ascorbic acid and itsderivatives, especially ascorbyl glucoside; and plant extracts, inparticular extracts of liquorice, of mulberry, of skullcap and of Bacopamonnieri, without this list being limiting.

Pro-pigmenting agents that may be mentioned include the extract ofburnet (Sanguisorba officinalis) sold by the company Maruzen, andextracts of chrysanthemum (Chrysanthemum morifolium).

3. Anti-Glycation Agent

The term “anti-glycation agent” means a compound for preventing and/orreducing the glycation of skin proteins, in particular of dermalproteins such as collagen.

Examples of anti-glycation agents are plant extracts of the Ericaceafamily, such as an extract of blueberry (Vaccinium angustifolium);ergothioneine and its derivatives; and hydroxystilbenes and theirderivatives, such as resveratrol and 3,3′,5,5′-tetrahydroxystilbene.These anti-glycation agents are described in patent applications FR 2802 425, FR 2 810 548, FR 2 796 278 and FR 2 802 420, respectively.Resveratrol is particularly preferred for use in this invention.

4. NO-Synthase Inhibitor

Examples of NO-synthase inhibitors that are suitable for use in thepresent invention especially comprise a plant extract of the speciesVitis vinifera which is sold especially by the company Euromed under thename “Leucocyanidines de raisins extra”, or by the company Indena underthe name Leucoselect®, or finally by the company Hansen under the name“Extrait de marc de raisin”; a plant extract of the species Oleaeuropaea which is preferably obtained from olive tree leaves and is soldespecially by the company Vinyals in the form of a dry extract, or bythe company Biologia & Technologia under the trade name Eurol BT; and aplant extract of the species Gingko biloba which is preferably a dryaqueous extract of this plant sold by the company Beaufour under thetrade name “Gingko biloba extrait standard”.

5. Anti-Seborrhoeic Agent

When the composition according to the invention comprises ananti-seborrhoeic agent such as a 5α-reductase inhibitor, this agent maybe chosen especially from:

-   -   retinoids, and in particular retinol;    -   sulfur and sulfur derivatives;    -   zinc salts such as zinc lactate, gluconate, pidolate,        carboxylate, salicylate and/or cysteate;    -   selenium chloride;    -   vitamin B6 or pyridoxine;    -   mixture of capryloyl glycine, sarcosine and extract of        Cinnamomum zeylanicum sold especially by the company SEPPIC        under the trade name Sepicontrol A5®;    -   an extract of Laminaria saccharina sold especially by the        company SECMA under the trade name Phiorogine®;    -   an extract of Spiraea ulmaria sold especially by the company        Silab under the trade name Sebonormine®;    -   plant extracts from the species Arnica montana, Cinchona        succirubra, Eugenia caryophyllata, Humulus lupulus, Hypericum        perforatum, Mentha piperita, Rosmarinus officinalis, Salvia        oficinalis and Thymus vulgaris, all sold, for example, by the        company Maruzen;    -   an extract of Serenoa repens sold especially by the company        Euromed;    -   plant extracts of the genus Silybum;    -   plant extracts containing sapogenins and in particular extracts        of diosgenin-rich or hecogenin-rich Dioscorea plants; and    -   extracts of Eugenia caryophyllata containing eugenol or eugenyl        glucoside.        6. Agent for Stimulating the Synthesis of Dermal or Epidermal        Macromolecules and/or for Preventing their Degradation

Among the active agents for stimulating dermal macromolecules or forpreventing their degradation, mention may be made of those that act:

-   -   either on collagen synthesis, such as extracts of Centella        asiatica; asiaticosides and derivatives; ascorbic acid or        vitamin C and its derivatives; synthetic peptides such as iamin,        biopeptide CL or the palmitoyloligopeptide sold by the company        Sederma; peptides extracted from plants, such as the soybean        hydrolysate sold by the company Coletica under the trade name        Phytokine®; and plant hormones such as auxins;    -   or on elastin synthesis, such as the extract of Saccharomyces        cerivisiae sold by the company LSN under the trade name        Cytovitin®; and the extract of the alga Macrocystis pyrifera        sold by the company SECMA under the trade name Kelpadelie®;    -   or on glycosaminoglycan synthesis, such as the product of        fermentation of milk with Lactobacillus vulgaris, sold by the        company Brooks under the trade name Biomin Yogourth®; the        extract of the brown alga Padina pavonica sold by the company        Alban Müller under the trade name HSP3®; and the extract of        Saccharomyces cerevisiae available especially from the company        Silab under the trade name Firmalift® or from the company LSN        under the trade name Cytovitin®;    -   or on fibronectin synthesis, such as the extract of the        zooplankton Salina sold by the company Seporga under the trade        name GP4G®;        the yeast extract available especially from the company Alban        Müller under the trade name Drieline®; and the palmitoyl        pentapeptide sold by the company Sederma under the trade name        Matrixil®;    -   or on the inhibition of metalloproteases (MMP), such as, more        particularly, MMP 1, 2, 3 or 9. Mention may be made of:        retinoids and derivatives, oligopeptides and lipopeptides,        lipoamino acids, the malt extract sold by the company Coletica        under the trade name Collalift®; extracts of blueberry or of        rosemary; lycopene; isoflavones, their derivatives or plant        extracts containing them, in particular extracts of soybean        (sold, for example, by the company Ichimaru Pharcos under the        trade name Flavosterone SB®), of red clover, of flax, of kakkon,        or of sage;    -   or on the inhibition of serine proteases such as leukocyte        elastase or cathepsin G. Mention may be made of: the peptide        extract of Leguminosa seeds (Pisum sativum) sold by the company        LSN under the trade name Parelastyl®; and heparinoids and        pseudodipeptides such as        {2-[acetyl(3-trifluoromethylphenyl)amino]-3-methylbutyrylamino}acetic        acid.

Among the active agents that stimulate epidermal macromolecules, such asfillagrin and keratins, mention may be made especially of the extract oflupin sold by the company Silab under the trade name Structurine®; theextract of beech Fagus sylvatica buds sold by the company Gattefosseunder the trade name Gatuline®; and the extract of the zooplanktonSalina sold by the company Seporga under the trade name GP4G®.

7. Agent for Stimulating Fibroblast or Keratinocyte Proliferation and/orKeratinocyte Differentiation

The agents for stimulating fibroblast proliferation that may be used inthe composition according to the invention may be chosen, for example,from plant proteins or polypeptides, extracted especially from soybean(for example an extract of soybean sold by the company LSN under thename Eleseryl SH-VEG 8® or sold by the company Silab under the tradename Raffermine®); and plant hormones such as giberrellins andcytokinins.

The agents for stimulating keratinocyte proliferation that may be usedin the composition according to the invention especially compriseretinoids such as retinol and its esters, including retinyl palmitate;phloroglucinol; extracts of walnut cakes sold by the company Gattefosse;and extracts of Solanum tuberosum sold by the company Sederma.

The agents for stimulating keratinocyte differentiation comprise, forexample, minerals such as calcium; the extract of lupin sold by thecompany Silab under the trade name Photopreventine®; sodium β-sitosterylsulfate sold by the company Seporga under the trade name Phytocohesine®;and the extract of corn sold by the company Solabia under the trade namePhytovityl®; and lignans such as secoisolariciresinol.

8. Muscle Relaxant or Dermo-Decontracting Agent

Among the muscle relaxants or dermo-decontracting agents that may beused in the composition according to the invention the following deserveparticular mention: alverine and its salts, manganese gluconate,Diazepam, Argireline hexapeptide R sold by the company Lipotec, certainsecondary and tertiary carbonyl amines, adenosine, sapogenins andnatural extracts, in particular of wild yam, containing them, and alsoextracts of Boswellia serrata.

9. Antimicrobial Agent

The antimicrobial agents that may be used in the composition accordingto the invention may be chosen especially from2,4,4′-trichloro-2′-hydroxydiphenyl ether (or triclosan),3,4,4′-trichlorobanilide, phenoxyethanol, phenoxypropanol,phenoxyisopropanol, hexamidine isethionate, metronidazole and its salts,micronazole and its salts, itraconazole, terconazole, econazole,ketoconazole, saperconazole, fluconazole, clotrimazole, butoconazole,oxiconazole, sulfaconazole, sulconazole, terbinafine, ciclopirox,ciclopiroxolamine, undecylenic acid and its salts, benzoyl peroxide,3-hydroxybenzoic acid, 4-hydroxybenzoic acid, phytic acid,N-acetyl-L-cysteine acid, lipoic acid, azelaic acid and its salts,arachidonic acid, resorcinol, 2,4,4′-trichloro-2′-hydroxydiphenyl ether,3,4,4′-trichlorocarbanalide, octopirox, octoxyglycerine,octanoylglycine, caprylyl glycol, 10-hydroxy-2-decanoic acid,dichlorophenylimidazole dioxolane and its derivatives described inpatent WO 93/18743, farnesol and phytosphingosines, and mixturesthereof.

The preferred antimicrobial agents are triclosan, phenoxyethanol,octoxyglycerine, octanoylglycine, 10-hydroxy-2-decanoic acid, caprylylglycol, farnesol and azelaic acid.

10. Tensioning Agent

The term “tensioning agent” means a compound capable of exerting tensionon the skin, the effect of which is to temporarily fade outirregularities on the skin's surface, such as wrinkles and fine lines.

Among the tensioning agents that may be used in the compositionaccording to the present invention, mention may be made especially of:

(1) synthetic polymers such as polyurethane latices or acrylic-siliconelatices, in particular those described in patent application EP-1 038519, such as a propylthio(polymethyl acrylate), propylthio(polymethylmethacrylate) and propylthio(polymethacrylic acid) graftedpolydimethylsiloxane, or alternatively a propylthio(polyisobutylmethacrylate) and propylthio(polymethacrylic acid) graftedpolydimethylsiloxane. Such grafted silicone polymers are sold especiallyby the company 3M under the trade names VS 80, VS 70 or LO21.(2) polymers of natural origin, especially (a) polyholosides, forexample (i) in the form of starch derived especially from rice, corn,potato, cassava, pea, Triticum aestivum wheat, oat, etc. or (ii) in theform of carrageenans, alginates, agars, gelans, cellulose-based polymersand pectins, advantageously as an aqueous dispersion of gelmicroparticles, and (b) latices consisting of shellac resin, sandaracgum, dammar resins, elemi gums, copal resins and cellulose-basedderivatives, and mixtures thereof,(3) plant proteins and protein hydrolysates, in particular from corn,rye, Triticum aestivum wheat, buckwheat, sesame, spelt, pea, bean,lentil, soybean and lupin,(3) mixed silicates, especially phyllosilicates and in particularLaponites,(4) wax microparticles chosen, for example, from carnauba wax,candelilla wax and alfalfa wax,(5) colloidal particles of mineral filler with a number-average diameterof between 0.1 and 100 nm and preferably between 3 and 30 nm, chosen,for example, from: silica, silica-alumina composites, cerium oxide,zirconium oxide, alumina, calcium carbonate, barium sulfate, calciumsulfate, zinc oxide and titanium dioxide.

11. Anti-Pollution Agent or Free-Radical Scavenger

The term “anti-pollution agent” means any compound capable of trappingozone, monocyclic or polycyclic aromatic compounds such as benzopyreneand/or heavy metals such as cobalt, mercury, cadmium and/or nickel. Theterm “free-radical scavenger” means any compound capable of trappingfree radicals.

As ozone-trapping agents that may be used in the composition accordingto the invention, mention may be made in particular of vitamin C and itsderivatives including ascorbyl glucoside; phenols and polyphenols, inparticular tannins, ellagic acid and tannic acid; epigallocatechin andnatural extracts containing it; extracts of olive tree leaf; extracts oftea, in particular of green tea; anthocyans; extracts of rosemary;phenol acids, in particular chorogenic acid; stilbenes, in particularresveratrol; sulfur-containing amino acid derivatives, in particularS-carboxymethylcysteine; ergothioneine; N-acetylcysteine; chelatingagents, for instance N,N′-bis(3,4,5-trimethoxybenzyl)ethylenediamine orone of its salts, metal complexes or esters; carotenoids such ascrocetin; and various starting materials, for instance the mixture ofarginine, histidine ribonucleate, mannitol, adenosine triphosphate,pyridoxine, phenylalanine, tyrosine and hydrolysed RNA, sold byLaboratoires Serobiologiques under the trade name CPP LS 2633-12F®, thewater-soluble fraction of corn sold by the company Solabia under thetrade name Phytovityl®, the mixture of extract of fumitory and ofextract of lemon sold under the name Unicotrozon C-49® by the companyInduchem, and the mixture of extracts of ginseng, of apple, of peach, ofwheat and of barley, sold by the company Provital under the trade namePronalen Bioprotect®.

As agents for trapping monocyclic or polycyclic aromatic compounds,which may be used in the composition according to the invention, mentionmay be made in particular of tannins such as ellagic acid; indolederivatives, in particular 3-indolecarbinol; extracts of tea, inparticular of green tea, extracts of water hyacinth or Eichhorniacrassipes; and the water-soluble fraction of corn sold by the companySolabia under the trade name Phytovityl®.

Finally, as heavy-metal-trapping agents that may be used in thecomposition according to the invention, mention may be made inparticular of chelating agents such as EDTA, the pentasodium salt ofethylenediaminetetramethylenephosphonic acid, andN,N′-bis(3,4,5-trimethoxybenzyl)ethylenediamine or one of the salts,metal complexes or esters thereof; phytic acid; chitosan derivatives;extracts of tea, in particular of green tea; tannins such as ellagicacid; sulfur-containing amino acids such as cysteine; extracts of waterhyacinth (Eichhornia crassipes); and the water-soluble fraction of cornsold by the company Solabia under the trade name Phytovityl®.

The free-radical scavengers that may be used in the compositionaccording to the invention comprise, besides certain anti-pollutionagents mentioned above, vitamin E and its derivatives such as tocopherylacetate; bioflavonoids; coenzyme Q10 or ubiquinone; certain enzymes, forinstance catalase, superoxide dismutase, lactoperoxidase, glutathioneperoxidase and quinone reductases; glutathione; benzylidenecamphor;benzylcyclanones; substituted naphthalenones; pidolates; phytanetriol;gamma-oryzanol; lignans; and melatonin.

12. Calmatives

As calmatives that may be used in the composition according to theinvention, mention may be made of: pentacyclic triterpenes and extractsof plants (e.g.: Glycyrrhiza glabra) containing them, for instanceβ-glycyrrhetinic acid and salts and/or derivatives thereof(glycyrrhetinic acid monoglucoronide, stearyl glycyrrhetinate or3-stearoyloxyglycyrrhetic acid), ursolic acid and its salts, oleanolicacid and its salts, betulinic acid and its salts, an extract of Paeoniasuffruticosa and/or lactiflora, salicylic acid salts and in particularzinc salicylate, the phycosaccharides from the company Codif, an extractof Laminaria saccharina, canola oil, bisabolol and camomile extracts,allantoin, Sepivital EPC (phosphoric diester of vitamins E and C) fromSEPPIC, omega-3 unsaturated oils such as musk rose oil, blackcurrantoil, ecchium oil, fish oil, plankton extracts, capryloylglycine,Seppicalm VG (sodium palmitoylproline and Nymphea alba) from SEPPIC, anextract of Pygeum, an extract of Boswellia serrata, an extract ofCentipeda cunnighami, an extract of Helianthus annuus, an extract ofLinum usitatissimum, tocotrienols, extracts of Cola nitida, piperonal,an extract of clove, an extract of Epilobium angustifolium, Aloe vera,an extract of Bacopa moniera, phytosterols, cortisone, hydrocortisone,indomethacin and betamethasone.

13. Agents Acting on the Capillary Circulation

The active agents acting on the capillary circulation (vasoprotective orvasodilating agents) may be selected from the group consisting offlavonoids, ruscogenins, esculosides, escin extracted from common horsechestnut, nicotinates, heperidine methyl chalcone, essential oils oflavender or of rosemary, and extracts of Ammi visnaga.

The invention will now be illustrated by the non-limiting examples thatfollow. In these examples, the amounts are indicated as percentages byweight.

EXAMPLES Example 1 Cosmetic Compositions

A (compar- O/W emulsions ative) B C D Xanthan gum 0.20% 0.20% 0.20%0.20% Crosslinked poly(2-acrylamido-2- 0.40% 0.40% 0.40% 0.40%methyl-propanesulfonic acid) Cyclohexasiloxane 10.0% 10.0% 10.0% 10.0%Sodium hydroxide 0.01% 0.01% 0.01% 0.01% Glycerol 5.00% 5.00% 5.00%5.00% Stearyl alcohol 1.00% 1.00% 1.00% 1.00% Polyoxyethylene glycerylstearate 2.00% 2.00% 2.00% 2.00% (100 OE) Dimyristyl tartrate, cetearylalcohol, 1.50% 1.50% 1.50% 1.50% oxyethylenated (7 OE) C¹²⁻¹⁵ fattyalcohols and oxyethylenated (25 OE) and oxypropylenated (25 OE) laurylalcohol Spherical particles of crosslinked 5.00% organopolysiloxane ⁽¹⁾Hemispherical particles of 5.00% crosslinked organopolysiloxane ⁽²⁾Hemispherical particles of 5.00% crosslinked organopolysiloxane ⁽³⁾Hemispherical particles of 5.00% crosslinked organopolysiloxane ⁽⁴⁾Preserving agents 0.70% 0.70% 0.70% 0.70% Water qs qs qs qs  100%  100% 100%  100% ⁽¹⁾ Spherical particles of diameter 3.2 μm consisting of adimethiconol/silsesquioxane copolymer ⁽²⁾ Particles consisting of thecrosslinked organosilicone TAK-110 (methylsilanol/silicate crosslinkedpolymer) from the company Takemoto Oil & Fat, in the form of a bowl 2.5μm wide, 1.5 μm high and 350 nm thick ⁽³⁾ Particles consisting of thecrosslinked organosilicone TAK-110 (methylsilanol/silicate crosslinkedpolymer) from the company Takemoto Oil & Fat, in the form of a bowl 2.5μm wide, 1.5 μm high and 600 nm thick ⁽⁴⁾ Particles consisting of thecrosslinked organosilicone TAK-110 (methylsilanol/silicate crosslinkedpolymer) from the company Takemoto Oil & Fat.

These compositions are prepared in a manner that is conventional for aperson skilled in the art, by adding, with stirring, the oily phaseheated to 65° C. to the hot aqueous phase.

Example 2 In Vitro Evaluation of the Optical Properties

The matt effect obtained with compositions B to D according to theinvention, and with composition A given as a comparative example, wasmeasured using a contrast card (Prufkarte type 24/5-250 cm²) sold by thecompany Erichsen. The composition was spread at a rate of 2 mg/cm² usinga mechanical film spreader. The composition was then dried overnight ata temperature of 37° C., and the reflection was then measured using agonioreflectometer. The result obtained is the ratio R between thespecular reflection and the diffuse reflection. The value of R isproportionately smaller the greater the matting effect.

Composition A B C D R 2.00 ± 0.09 0.85 ± 0.10 0.88 ± 0.02 0.55 ± 0.05

These in vitro results show that with a 5% (active material)concentration of hemispherical particles of organopolysiloxane, the mattresult obtained is very much superior to that obtained with thecomparative formulation containing organosilicon-based sphericalparticles.

Example 3 In Vivo Evaluation

The matting effect and the cosmetic aspects of a formulationcorresponding to composition B of Example 1, but containing 8% ofhemispherical particles of organopolysiloxane instead of 5%, wereevaluated by a panel of seven women with greasy skin. It was judged thatthis composition made the skin matt and gave it a fine grain, the poresappearing less dilated and the complexion more unified. A soft-focuseffect on the defects was observed.

Example 4 In Vivo Evaluation

The optical effects on the skin of a composition corresponding tocomposition B of Example 1, but containing 8% by weight of hemisphericalparticles of crosslinked organopolysiloxane obtained under the tradename NLK-506 from Takemoto Oil and Fat, were evaluated on a panel of sixwomen with greasy skin and having irregularities of the microrelief.

It was observed that the test composition instantaneously matted thehighlights on the surface of the skin and reduced the visibility of themicrorelief by making the grain of the skin fine, the pores appearingless dilated.

The above written description of the invention provides a manner andprocess of making and using it such that any person skilled in this artis enabled to make and use the same, this enablement being provided inparticular for the subject matter of the appended claims, which make upa part of the original description and including a composition in theform of an emulsion comprising, in a physiologically acceptable medium,portions of hollow spheres consisting of organosilicon-based material,the spheres having a mean diameter ranging from 0.05 to 10 μm. Anotherembodiment of the invention fully described and enabled include acosmetic process for fading out skin surface defects using the inventioncompositions. In preferred embodiments the amount of invention hollowsphere portions present in the invention compositions, and/or the amountapplied in the invention processes, is an amount sufficient toeffectively treat, prevent, or treat or prevent the appearance of, skinsurface defects, aged skin, greasy or combination skin, skin sheen, poreappearance, shadows under the eyes, marks, wrinkles and/or fine lines.

As used above, the phrases “selected from the group consisting of,”“chosen from,” and the like include mixtures of the specified materials.

All references, patents, applications, tests, standards, documents,publications, brochures, texts, articles, etc. mentioned herein areincorporated herein by reference. Where a numerical limit or range isstated, the endpoints are included. Also, all values and subrangeswithin a numerical limit or range are specifically included as ifexplicitly written out.

The above description is presented to enable a person skilled in the artto make and use the invention, and is provided in the context of aparticular application and its requirements. Various modifications tothe preferred embodiments will be readily apparent to those skilled inthe art, and the generic principles defined herein may be applied toother embodiments and applications without departing from the spirit andscope of the invention. Thus, this invention is not intended to belimited to the embodiments shown, but is to be accorded the widest scopeconsistent with the principles and features disclosed herein.

1. A composition in the form of an emulsion comprising, in aphysiologically acceptable medium, portions of hollow spheres consistingof organosilicon-based material, the spheres having a mean diameterranging from 0.05 to 10 μm.
 2. A composition according to claim 1,wherein the portions of hollow spheres are obtained according to aprocess comprising: (a) introducing into an aqueous medium, in thepresence of a hydrolysis catalyst, and optionally of a surfactant, acompound (I) of formula SiX₄ and a compound (II) of formula RSiY₃, inwhich X and Y independently denote a C₁-C₄ alkoxy group, an alkoxyethoxygroup containing a C₁-C₄ alkoxy group, a C₂-C₄ acyloxy group, anN,N-dialkylamino group containing a C₁-C₄ alkyl group, a hydroxyl group,a halogen atom or a hydrogen atom, and R denotes an organic groupcomprising a carbon atom directly linked to the silicon atom; and (b)placing the mixture resulting from step (a) in contact with an aqueoussolution containing at least one polymerization catalyst and optionallyat least one surfactant, at a temperature of between 30 and 85° C., forat least two hours.
 3. A composition according to claim 2, wherein thecompound of formula (I) is selected from the group consisting of:tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane,trimethoxyethoxysilane, tributoxyethoxysilane, tetraacetoxysilane,tetraprop oxysilane, tetraacetoxysilane, tetra(dimethylamino)silane,tetra(diethylamino)silane, silane tetraol, chlorosilane triol,dichlorodisilanol, tetrachlorosilane, chlorotrihydrogenosilane andmixtures thereof.
 4. A composition according to claim 2, wherein thecompound of formula (II) comprises an unreactive organic group R and isselected from the group consisting of: methyltrimethoxysilane,ethyltriethoxysilane, propyltributoxysilane, butyltributoxysilane,phenyltrimethoxyethoxysilane, methyltributoxyethoxysilane,methyltriacetoxysilane, methyltripropoxysilane, methyltriacetoxysilane,methyltri(dimethylamino)silane, methyltri(diethylamino)silane,methylsilane triol, methylchlorodisilanol, methyltrichlorosilane,methyltrihydrogenosilane and mixtures thereof.
 5. A compositionaccording to claim 2, wherein the compound of formula (II) comprises areactive organic group R and is selected from the group consisting of:silanes containing an epoxy group; silanes containing a (meth)acryloxygroup; silanes containing an alkenyl group; silanes containing amercapto group; silanes containing an aminoalkyl group; silanescontaining a haloalkyl group; silanes containing a glyceroxy group;silanes containing a ureido group; silanes containing a cyano group, andmixtures thereof.
 6. A composition according to claims 2, wherein Xand/or Y denotes a C₁-C₄ alkoxy group.
 7. A composition according toclaim 2, wherein compound (I) is tetraethoxysilane.
 8. A compositionaccording to claim 2, wherein compound (II) is methyltrimethoxysilane.9. A composition according to claim 2, wherein, in (a), the molar ratioof compound (I) to compound (II) ranges from 30:70 to 50:50.
 10. Acomposition according to claim 9, wherein the molar ratio of compound(I) to compound (II) ranges from 35:65 to 45:55.
 11. A compositionaccording to claim 8, wherein the molar ratio of compound (I) tocompound (II) is 40:60.
 12. A composition according to claim 2, whereinthe weight ratio of water in said aqueous medium to the total amount ofcompounds (I) and (II) ranges from 10:90 to 70:30 in step (a).
 13. Acomposition according to claim 2, wherein the hydrolysis andpolymerization catalysts are independently selected from the groupconsisting of sodium hydroxide, sodium carbonate, acetic acid, sodiumdodecylbenzenesulfonate, hydrochloric acid and mixtures thereof.
 14. Acomposition according to claim 2, wherein the surfactant is sodiumdodecylbenzenesulfonate.
 15. A composition according to claim 1, whereinthe portions of hollow spheres comprise a crosslinked polysiloxane ofthree-dimensional structure consisting of units of formula (I): SiO₂ andof formula (II): R¹SiO_(1.5) in which R¹ denotes an organic groupcontaining a carbon atom directly linked to the silicon atom.
 16. Acomposition according to claim 15, wherein R¹ is an unreactive organicgroup selected from the group consisting of: a methyl, ethyl, propyl,butyl group or a phenyl group.
 17. A composition according to claim 15,wherein R¹ is a reactive organic group selected from the groupconsisting of: an epoxy group, a (meth)acryloxy group, an alkenyl group,a mercaptoalkyl, aminoalkyl or haloalkyl group, a glyceroxy group, aureido group or a cyano group, containing from 2 to 6 carbon atoms. 18.A composition according to claim 16, wherein R¹ denotes a methyl group.19. A composition according to claim 1, wherein the portions of hollowspheres have a shape formed (in longitudinal cross section) from a smallinner arc (11), a large outer arc (21) and segments (31) linking theends of the respective arcs, the width (W1) between the two ends of thesmall inner arc (11) ranging from 0.01 to 8 μm on average, the width(W2) between the two ends of the large outer arc (21) ranging from 0.05to 10 μm on average and the height (H) of the large outer arc (21)ranging from 0.015 to 8 μm on average.
 20. A composition according toclaim 19, wherein the segments (31) have a length (W2−W1)/2 ranging from0.05 to 1 μm.
 21. A composition according to claim 19, wherein the ratioRa of the width W2 to the thickness (W2−W1)/2 is at least
 3. 22. Acomposition according to claim 21, wherein the ratio Ra of the width W2to the thickness (W2−W1)/2 is greater than
 5. 23. A compositionaccording to claim 22, wherein the ratio Ra of the width W2 to thethickness (W2−W1)/2 is greater than
 10. 24. A composition according toclaim 23, wherein the ratio Ra of the width W2 to the thickness(W2−W1)/2 is greater than
 20. 25. A composition according to claim 1,wherein the amount of portions of hollow spheres represents from 0.5% to10% of the total weight of the composition.
 26. A composition accordingto claim 1, wherein said composition is in the form of an O/W emulsion.27. A composition according to claim 1, further comprising at least onevolatile oil.
 28. A composition according to claim 27, wherein thevolatile oil is selected from the group consisting of: cyclic or linearsilicones containing from 2 to 6 silicon atoms, branched hydrocarbons,volatile perfluoroalkanes, perfluoromorpholine derivatives, and mixturesthereof.
 29. A process for fading out skin surface defects, comprisingtopically applying to skin in need thereof the composition according toclaim
 1. 30. The process according to claim 29, wherein said process isa process to reduce the sheen of the skin and/or to fade out the pores,and wherein the amount of composition applied is an amount effective toreduce the sheen of the skin and/or to fade out the pores.
 31. Theprocess according to claim 29, wherein said process is a process totreat greasy or combination skin, and wherein the amount of compositionapplied is an amount effective to treat greasy or combination skin. 32.The process according to claim 30, wherein the composition furthercomprises at least one active agent selected from the group consistingof: desquamating agents, anti-seborrhoeic agents, antimicrobial agents,calmatives and mixtures thereof.
 33. The process according to claim 29,wherein said process is a process to fade out shadows under the eyes,marks, wrinkles and/or fine lines, and wherein the amount of compositionapplied is an amount effective to fade out shadows under the eyes,marks, wrinkles and/or fine lines.
 34. The process according to claim29, wherein the skin is aged skin.
 35. The process according to claim34, wherein the composition further comprises at least one active agentselected from the group consisting of: desquamating agents ormoisturizers; depigmenting or anti-pigmenting agents; anti-glycationagents; anti-NO agents; agents for stimulating the synthesis of dermalor epidermal macromolecules and/or for preventing their degradation;agents for stimulating fibroblast or keratinocyte proliferation and/orkeratinocyte differentiation; muscle relaxants or dermo-decontractingagents; free-radical scavengers or anti-pollution agents; tensioningagents; and agents acting on the capillary circulation.
 36. Thecomposition according to claim 1, wherein the composition comprises atleast one surfactant.
 37. The composition according to claim 27, whereinthe composition comprises at least one surfactant.